CN108417899A - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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Publication number
CN108417899A
CN108417899A CN201810129797.3A CN201810129797A CN108417899A CN 108417899 A CN108417899 A CN 108417899A CN 201810129797 A CN201810129797 A CN 201810129797A CN 108417899 A CN108417899 A CN 108417899A
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China
Prior art keywords
electrode
barrier layer
secondary battery
lithium secondary
penetration barrier
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Granted
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CN201810129797.3A
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CN108417899B (en
Inventor
赵镛显
金在雄
姜旼求
都永勋
金辉星
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SK On Co Ltd
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SK Innovation Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0459—Cells or batteries with folded separator between plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

The invention discloses a kind of lithium secondary battery, the lithium secondary battery includes：Multiple electrodes unit, each in multiple electrodes unit include first electrode, with the polar second electrode different from the polarity of first electrode and the separating layer being placed between first electrode and second electrode；And at least one ion penetration barrier layer, between adjacent electrode unit, the gas permeability of ion penetration barrier layer is less than the gas permeability of separating layer.

Description

Lithium secondary battery
Technical field
The present invention relates to a kind of lithium secondary batteries.More particularly, it relates to a kind of including multiple insulating layers and multiple The lithium secondary battery of conductive layer.
Background technology
According to the development of information and display technology, the secondary cell being repeatably charged and discharged has been widely used as The power supply of the electronic apparatus of field camera, mobile phone, laptop computer etc..Recently, just in kit It includes the battery pack of secondary cell and is used as the power supply of the environmentally friendly vehicle of such as hybrid vehicle.
Secondary cell includes such as lithium secondary battery, nickel-cadmium cell, Ni-MH battery.Lithium secondary battery is due to per unit weight High working voltage and energy density, high charge rate, the compact dimensioning etc. of amount and protrude.
For example, lithium secondary battery may include comprising cathode, the electrode assembly of anode and separating layer and dipping electrode group The electrolyte of part.Lithium secondary battery, which may further include, has for example bag-shaped shell.
Expand with the application range of lithium secondary battery, has needed it with long-life, high power capacity and stable Property.Recently, it has studied a kind of reduce since electric pole short circuit occurs when external object penetrates and causes the method for battery explosion.
For example, the Korean patent application publication that number of patent application is 10-2015-0045737 discloses a kind of wearing Quick release of energy, such as fuse conductive structure when thoroughly.
Invention content
According to aspects of the present invention, a kind of lithium secondary battery for the operation and electrical stability for having and improving is provided.
Accoding to exemplary embodiment, lithium secondary battery includes：Multiple electrodes unit, each packet in multiple electrodes unit It includes first electrode, with the polar second electrode different from the polarity of first electrode and be placed in first electrode and second electrode Between separating layer；And at least one ion penetration barrier layer, between adjacent electrode unit, ion penetration barrier layer Gas permeability be less than separating layer gas permeability.
In some embodiments, the porosity of ion penetration barrier layer is smaller than the porosity of separating layer.
In some embodiments, separating layer may include by polyethylene, polypropylene, Kynoar, polyethylene oxide or Polymer film prepared by least one of polyacrylonitrile, and ion penetration barrier layer may include polyester-based resin, poly- ammonia Ester base resin, polyimide-based resin, polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), filling At least one of polypropylene screen or aromatic polyamides of organic and/or inorganic materials.
In some embodiments, first electrode and second electrode are relative to each other about ion penetration barrier layer.
In some embodiments, each space between electrode unit can be arranged in ion penetration barrier layer.
In some embodiments, first electrode and second electrode along lithium secondary battery thickness direction alternately about from Sub- penetration barrier layer is relative to each other.
In some embodiments, lithium secondary battery may further include：Shell, accommodate electrod unit and ion infiltration resistance Barrier；Electrolyte injects in shell；And first electrode lug plate (tap) and second electrode lug plate, respectively from first electrode The outside of shell is extended to each in second electrode.
In some embodiments, ion penetration barrier layer can the thickness direction along lithium secondary battery in the housing with First electrode lug plate and second electrode lug plate are overlapped at least partly.
In some embodiments, electrode connection panel region can be limited between the end of electrode unit and shell, and The part of ion penetration barrier layer extends to electrode connection panel region.
In some embodiments, ion penetration barrier layer is in the extension side of first electrode lug plate and second electrode lug plate Upward length can be more than length of the separating layer on the extending direction of first electrode lug plate and second electrode lug plate.
In some embodiments, length of the separating layer in the width direction of lithium secondary battery can be more than lithium ion and permeate Length of the barrier layer in the width direction of lithium secondary battery.
In some embodiments, separating layer can by coupling part along thickness direction and width direction with zigzag shape Shape extends.
In some embodiments, first electrode may include the first collector and coated on the first collector first electricity Pole active material layer, second electrode may include the second collector and coated in the second electrode active material on the second collector Layer, and first electrode active material layer and second electrode active material layer can be respectively coated on the first collector and the second collection On two surfaces of fluid or single surface.
In some embodiments, the first electrode of contact ions penetration barrier layer may include being coated in the first collector First electrode active material layer on single surface, and the second electrode of contact ions penetration barrier layer may include being coated in Second electrode active material layer on the single surface of second collector.
In some embodiments, ion penetration barrier layer can be in direct contact the first collector or the second collector.
Exemplary embodiment according to the present invention can be that each electrode unit forms ion penetration barrier layer for use as wearing Saturating barrier layer.The penetrability and/or porosity of ion penetration barrier layer can be less than the diaphragm being included in electrode unit (separator) penetrability and/or porosity.Therefore, electrode unit can be stacked with being arranged in parallel so that work as external object The deterioration that fever can be effectively prevented when penetrating battery, be charged and discharged failure and battery operation.
Ion penetration barrier layer can expand be overlapped with electrode tabs, and can to avoid battery case side or The reduction of the battery reliability of end.
Description of the drawings
Fig. 1 is the schematic cross section for showing lithium secondary battery accoding to exemplary embodiment；
Fig. 2 is the schematic cross section for showing lithium secondary battery in accordance with some embodiments；
Fig. 3 is the schematic top plan view for showing lithium secondary battery in accordance with some embodiments；
Fig. 4 and Fig. 5 is the schematic cross section for showing lithium secondary battery in accordance with some embodiments；And
Fig. 6 and Fig. 7 is the schematic cross section for showing lithium secondary battery in accordance with some embodiments.
Specific implementation mode
Exemplary embodiment according to the present invention, provide it is a kind of when penetrating there is improved operational reliability Lithium secondary battery.Lithium secondary battery may include：Electrode unit, each in electrode unit include first electrode, have The polar second electrode different from the polarity of first electrode and the separating layer being placed between first electrode and second electrode；With And at least one ion penetration barrier layer between electrode unit.The penetrability of ion penetration barrier layer is smaller than separating layer Penetrability.
Hereinafter, the present invention is described in detail with reference to the accompanying drawings.However, it will be understood by those skilled in the art that carrying For describing this embodiment with reference to the accompanying drawings to further understand the spirit of the present invention, and it is not limited in specific implementation mode and institute Claimed subject matter disclosed in attached claim.
Fig. 1 is the schematic cross section for showing lithium secondary battery accoding to exemplary embodiment.Referring to Fig.1, lithium is secondary Battery may include electrode assembly (for example, jelly-roll) and ion penetration barrier layer 150 containing multiple electrodes unit.
Electrode assembly may include the electrode unit 140 of lamination or stacking.Each electrode unit 140 may include about point The first electrode 110 relative to each other of absciss layer 120 and second electrode 130.
First electrode 110 may include the first collector 115 and the first electrode activity being formed on the first collector 115 Material layer 112.For example, first electrode 110 may be used as the cathode of lithium secondary battery.
First collector 115 may include the metal that can not be reacted in the voltage range of lithium secondary battery, and It can easily be coated by electrode active material.For example, the first collector 115 may include stainless steel, nickel, aluminium, titanium or its conjunction Gold；Or the aluminium or stainless steel that can be surface-treated by carbon, nickel, titanium, silver etc..In some embodiments, the first afflux Body 115 may be used as cathode current collector, and may include aluminum or aluminum alloy.
First electrode active material layer 112 may include such as active material of cathode.In this case, first electrode is lived Property material layer 112 may include lithium cobalt base oxide, lithium nickel-based oxide, lithium manganese-base oxide, lithium-vanadium base oxide etc. Lithium metal oxide based active material.
First electrode active material layer 112 can be formed at least one surface of the first collector 115.For example, such as Shown in Fig. 1, first electrode active material layer 112 can be formed in the top surface and bottom surface of the first collector 115.
In some embodiments, including the electrode slurry of first electrode active material can be coated in the first collector 115 At least one surface on, it is dry and using roll pressing to form first electrode 110.Electrode slurry can be by by first electrode Active material is mixed in a solvent together with such as binder, conductive additive and/or dispersant to prepare.
Binder may include such as Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP), Kynoar (PVDF), organic based binder of polyacrylonitrile, polymethyl methacrylate etc., or such as can be with such as carboxymethyl cellulose (CMC) SBR styrene butadiene rubbers (SBR) that thickener is used together contain water based adhesive.
Conductive additive can be added to promote the electron mobility between electrode.For example, conductive additive may include The carbon-based material of graphite, carbon black, graphene, carbon nanotube etc., and/or such as tin, tin oxide, titanium oxide, such as LaSrCoO3Or LaSrMnO3Perovskite material metal_based material.
Solvent may include such as n-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetylamide, N, N- Dimethylamino propylamine, ethylene oxide, the nonaqueous solvents of tetrahydrofuran (THF) etc..
Second electrode 130 may include the second collector 135 and the second electrode activity being formed on the second collector 135 Material layer 132.For example, second electrode 130 may be used as the anode of lithium secondary battery.
For example, the second collector 135 may include stainless steel, nickel, aluminium, titanium or its alloy；Or can by carbon, nickel, The aluminium or stainless steel that titanium, silver etc. are surface-treated.In some embodiments, the second collector 135 may be used as anode current collector Body, and may include copper or copper alloy.
Second electrode active material layer 132 may include such as active material of positive electrode.In this case, second electrode is lived Property material layer 132 may include such as crystalline carbon, amorphous carbon, carbon complex (carbon complex) or carbon fiber is carbon-based Material, lithium alloy, silicon, tin etc..Amorphous carbon may include hard carbon, coke, carbonaceous mesophase spherules (MCMB), intermediate phase pitch-based Carbon fiber (MPCF) etc..Crystalline carbon may include graphite-based material, such as natural graphite, graphitized coke, graphitization MCMB, stone Inkization MPCF etc..Lithium alloy may further include aluminium, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium and/or indium.
Second electrode active material layer 132 can be formed at least one surface of the second collector 135.In some realities It applies in example, as shown in Figure 1, second electrode active material layer 132 can be formed in the top surface and bottom surface of the second collector 135 On.Second electrode active material layer 132 can by with first electrode active material layer 112 is essentially identical or similar technique come It is formed.
First electrode 110 and second electrode 130 can be separately positioned in the top surface and bottom surface of separating layer 120.Point Absciss layer 120 may be used as preventing diaphragm short-circuit between first electrode 110 and second electrode 130, and be also used as first Lithium ion path between electrode 110 and second electrode 130.
Separating layer 120 can be formed by insulating materials and porous material, and ion can pass through insulating materials and porous material It is shifted between first electrode 110 and second electrode 130.It is, for example, possible to use with high ion permeability and mechanical strength Insulate thin resin film.The non-limiting example of material for separating layer 120 may include such as polyacrylic alkylene polymerization The sheet material of object including glass fibre or polyethylene, the polymer film etc. comprising adhesive-bonded fabric or inorganic material.It is such as poly- in use When closing electrolyte of the solid electrolyte of object as lithium secondary battery, solid electrolyte is also used as separating layer.
In embodiment, separating layer 120 may include the multilayer prepared by polyethylene film, polypropylene screen or combinations thereof form Film, or the polymer by preparations such as Kynoar, polyethylene oxide, polyacrylonitrile or Kynoar hexafluoropropylene copolymers Film.
Multiple electrodes unit 140 with element as described above and structure can be stacked, and it is at least one from Sub- penetration barrier layer 150 can be placed between electrode unit 140 adjacent to each other.In the exemplary embodiment, as shown in Figure 1, Each space between electrode unit 140 can be inserted in ion penetration barrier layer 150.For example, first to fourth electrode unit 140a, 140b, 140c and 140d can be stacked, and first to third ion penetration barrier layer 150a, 150b and 150c It is inserted between electrode unit.
In the exemplary embodiment, ion penetration barrier layer 150 may include insulating materials, the gas permeability of the insulating materials (or air permeability) is less than the gas permeability (or air permeability) of separating layer 120.In addition, ion penetration barrier layer 150 may include resin Material, the porosity of the resin material are less than the porosity of separating layer 120.
In some embodiments, ion penetration barrier layer 150 may include polyester-based resin, polyurethane-based resin, polyamides Imido grpup resin, polymethyl methacrylate (PMMA), fills organic and/or inorganic materials at polyethylene terephthalate (PET) Polypropylene screen, aromatic polyamides etc..These can be used alone or are used in the form of a combination thereof.In embodiment, ion permeates Barrier layer 150 may include the high heat resistance polymer with about 300 DEG C or more of fusing point.
In some embodiments, the gas permeability of separating layer 120 can be in about 1/6cc/sec to the range of about 10cc/sec It is interior.The gas permeability of ion penetration barrier layer 150 can be about 1/20cc/sec or less.In some embodiments, according to separating layer The gas permeability of 120 material, separating layer 120 can be reduced to about 1/20cc/sec or less (for example, about 1/30cc/sec).At this Kind in the case of, for example, the gas permeability of ion penetration barrier layer 150 can be about 1/40cc/sec or less or about 1/50cc/sec with Under.
Gas permeability can pass through the time needed for film or resin layer sample according to the air of the specific quantity with constant pressure To measure.For example, gas permeability can be based on using such as Gurley such as standard ASTM D726, BS5926, ISO 3636/5 The air permeability tester of densometer measures.
As described above, the gas permeability and/or porosity of ion penetration barrier layer 150 can be less than the ventilative of separating layer 120 Property and/or porosity, therefore the ionic conductivity of ion penetration barrier layer 150 and/or ion permeability can be less than separating layer 120 ionic conductivity and/or ion permeability.Therefore, it can be prevented by ion penetration barrier layer 150 between electrode unit Ion infiltration, ion diffusion or ionic conduction so that electrode unit 140 can substantially be divided by ion penetration barrier layer 150 From to be connected in parallel.In terms of the capacity of secondary cell, realize that being connected in parallel for electrode unit 140 will be advantageous.This Outside, when the external object through electrode component of such as nail or spicule, the ionic conduction between electrode unit 140 may quilt Blocking to can inhibit by penetrating caused fever, and is also prevented from and is charged/put caused by explosion or temperature raising Electric fault.
In addition, the ion penetration barrier layer 150 with low penetration and porosity also acts as blocking mass transfer or matter Measure the barrier layer of diffusion.It therefore, when breakthrough occurs, can be to avoid due to operation caused by the mass transfer between electrode unit Failure.
In some embodiments, the thickness of ion penetration barrier layer 150 can be in the range of about 10 μm to about 100 μm. If the thickness of ion penetration barrier layer 150 is less than about 10 μm, ion permeation barrier or electrode unit cannot be fully realized It is connected in parallel.If the thickness of ion penetration barrier layer 150 is more than about 100 μm, the capacity of the volume relative to secondary cell May excessively it reduce.
In embodiment, the thickness of separating layer 120 can be in the range of about 10 μm to about 30 μm.In view of each electrode The speed of service and capacity of unit, the thickness of separating layer 120 can be less than the thickness of ion penetration barrier layer 150.
In some embodiments, the electrode with opposed polarity can be relative to each other about ion penetration barrier layer 150.Example Such as, as shown in Figure 1, second electrode 130 can be arranged on ion penetration barrier layer 150, and first electrode 110 can be arranged 150 lower section of ion penetration barrier layer.For example, the top surface and bottom surface of ion penetration barrier layer 150 can be electric with second respectively Pole active material layer 132 and first electrode active material layer 112 contact.
Therefore, being connected in parallel for electrode unit can be highly reliably realized.
Fig. 2 is the schematic cross section for showing lithium secondary battery in accordance with some embodiments.With reference to Fig. 2, with ion In the electrode that penetration barrier layer 150 contacts, the single coating of electrode active material layers is formed on a current collector.
For example, can be omitted electrode activity material between ion penetration barrier layer 150 and collector 135 and collector 115 The bed of material 132 and electrode active material layers 112.In this case, the top surface and bottom surface of ion penetration barrier layer 150 can be with Directly contacted with collector 135 and collector 115.
In implementation described in Fig. 2, therefore accessible ion penetration barrier layer 150 is simultaneously less effective in terms of capacity increase Electrode active material layers can be omitted, so as to reduce the thickness of electrode assembly or entire battery.Accordingly it is possible to prevent Thickness or volume increase while capacity being made to reduce and minimize caused by adding ion penetration barrier layer 150.In addition, with from The adjacent electrode active material layers 112 of sub- penetration barrier layer 150 and 132 can be omitted, and be worn so as to extraly reduce to work as Mass transfer between electrode unit or ion-transfer when occurring thoroughly, and the event caused by burning can be more efficiently prevented from Barrier.
Fig. 3 is the schematic top plan view for showing lithium secondary battery in accordance with some embodiments.Fig. 4 and Fig. 5 is to show The schematic cross section of lithium secondary battery in accordance with some embodiments.
For example, Fig. 4 is the cross-sectional view along the line I-I' interceptions of Fig. 3.Fig. 5 is the cross of the line II-II' interceptions along Fig. 3 Sectional view.
For ease of description, the first electrode of electrode assembly and the diagram of second electrode are omitted in figure 3.Fig. 4 and Fig. 5 Shown in the quantity of electrode unit and ion penetration barrier layer be only exemplary, and can additionally increase.
Both direction perpendicular to one another is defined as first direction and second direction in terms of the plan view of Fig. 3.For example, first Direction can be the direction that the electrode tabs of secondary cell extend.Second direction can be the width direction of secondary cell.
With reference to Fig. 3, for example, electrode assembly and ion penetration barrier layer 150 can be contained in shell described with reference to Figure 1 In 200.Shell may include bag, tank etc..
In some embodiments, electrolyte solution can be injected into shell 200.Electrolyte solution may include as electricity Solve the packet nonaqueous electrolyte containing lithium salt and organic solvent of matter.Organic solvent may include propene carbonate (PC), carbonic acid Asia second Ester (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl propyl carbonate, dipropyl carbonate, Dimethyl sulfoxide, acetonitrile, dimethoxy-ethane, diethoxyethane, vinylene carbonate, sulfolane, gamma-butyrolacton, sulfurous acid Acrylic ester, tetrahydrofuran etc..These can be used alone or are used in the form of a combination thereof.
First electrode lug plate 110a can extend from the first collector 115 in a first direction.Second electrode lug plate 130a can extend from the second collector 135 in a first direction.
First electrode lug plate 110a and second electrode lug plate 130a can from the internal stretch of shell 200, and One and the part of second electrode lug plate can be exposed to the outside of shell 200.As shown in Fig. 2, first electrode lug plate 110a The same side of secondary cell or shell 200 can be located at second electrode lug plate 130a.However, first electrode lug plate 110a The opposite side of secondary cell or shell 200 can be located at each other with second electrode lug plate 130a.For example, first electrode lug plate 110a and second electrode lug plate 130a can be located at two ends on the first direction of shell 200.
First electrode lug plate 110a and second electrode lug plate 130a can be formed in be included in it is every in electrode assembly At a electrode unit 140.Multiple first electrode lug plate 110a and multiple second electrode lug plate 130a can be in shells 200 End welds together and extends to the outside of shell 200.
As shown in figure 3, ion penetration barrier layer 150 in the plan view can be with covering electrode group part, and it can at least portion Divide ground Chong Die with the electrode tabs 110a and 130a in shell 200.In some embodiments, ion penetration barrier layer 150 exists Length on first direction can be more than the length of separating layer 120 in a first direction.For example, in the plan view, ion infiltration Barrier layer 150 can be protruded from two ends of separating layer 120 in a first direction.
In embodiment, the length of separating layer 120 in a second direction can be more than ion penetration barrier layer 150 second Length on direction.For example, in the plan view, separating layer 120 can be in a second direction from the two of ion penetration barrier layer 150 A transverse part protrudes.
With reference to Fig. 4, the end of first electrode lug plate 110a and ion penetration barrier layer 150 can be at the end of electrode assembly It overlaps each other between portion and shell 200.Therefore, ion penetration barrier layer 150 may be used as electrode connection panel region (for example, by Dotted line indicate region) in and electrode assembly in penetrate barrier layer.
With reference to Fig. 5, separating layer 120 can be extended along the second direction and thickness direction of secondary cell with zigzag shape. For example, separating layer 120 may include in each electrode unit 140, and can continuously be extended through coupling part 120a For winding form.For example, ion penetration barrier layer 150 is inserted at each winding zone 160 of separating layer 120.
The width (for example, width in second direction) of ion penetration barrier layer 150 can be more than first electrode 110 and the The respective width of two electrodes 130.Therefore, penetrate barrier layer can at the end of electrode assembly and shell 200 by include from Sub- penetration barrier layer 150 and the setting of the insulation system of separating layer 120.
Fig. 6 and Fig. 7 is the schematic cross section for showing lithium secondary battery in accordance with some embodiments.For example, Fig. 6 and figure 7 be respectively along I-I' and III-III' interception schematic cross section.
Referring to figure 6 and figure 7, the electrode of identical polar can be relative to each other about ion penetration barrier layer 150.
For example, as shown in fig. 6, first electrode 110 can be relative to each other about the second ion penetration barrier layer 150b.At this In the case of kind, first electrode lug plate 110a can permeate in the electrode connection panel region being represented by the dotted line about the second ion Barrier layer 150b is relative to each other.In addition, the first electrode active material layer 112 being included in Different electrodes unit 140 can be with The top surface and bottom surface of second ion penetration barrier layer 150b contacts.
In addition, as shown in fig. 7, second electrode 130 can be oozed about the first ion penetration barrier layer 150a and third ion Each in saturating barrier layer 150c is relative to each other.In this case, second electrode lug plate 130a can refer to by dotted line About every in the first ion penetration barrier layer 150a and third ion penetration barrier layer 150c in the electrode connection panel region shown One opposite to each other.In addition, the second electrode active material layer 132 being included in Different electrodes unit 140 can with first from The top surface and bottom surface of sub- penetration barrier layer 150a and third ion penetration barrier layer 150c contact.
According to Fig. 6 and embodiment shown in Fig. 7, the electrode of identical polar can be about ion penetration barrier layer 150 each other Relatively.In embodiment, first electrode 110 and second electrode 130 can along secondary cell thickness direction alternately about Ion penetration barrier layer 150 is relative to each other.For example, second electrode 130 can be about third ion penetration barrier layer 150c each other Relatively, first electrode 110 can be relative to each other about the second ion penetration barrier layer 150b, and second electrode 130 can be about First ion penetration barrier layer 150a is relative to each other.
According to embodiment as described above, ion penetration barrier layer 150 may be used as collets, and the ion of the collets is led Ionic conductivity electrically than separating layer 120 is small so that the electrode of identical polar can be relative to each other.In this case, from Sub- penetration barrier layer 150 can be placed between the electrode tabs 110a that can be welded to one another and electrode tabs 130a.Therefore, Ion penetration barrier layer 150 can be used as penetrating barrier layer in electrode connection panel region, and be also used as welding guiding Part, welding support element or welding buffering pattern.
For example, ion penetration barrier layer 150 can increase the electrode tabs 110a being included in Different electrodes unit 140 With separated regions of the electrode tabs 130a in electrode connection panel region, and it is also used as the support element of welding process.
Hereinafter, propose preferred embodiment the present invention is more specifically described.It is only used however, providing following embodiment In illustrating the present invention, and those skilled in the relevant art will obviously understand, within the scope and spirit of this invention can be with It makes various changes and modifications.Such change and modification include fully in the following claims.
Example
By the LiNi as active material of cathode0.8Co0.1Mn0.1O2, as the carbon black of conductive additive and as binder Kynoar with 92:5:3 weight ratio is mixed to form cathode slurry.Cathode slurry is coated on aluminum substrate, then It is dried and suppresses to form cathode.
By will be used as the 92wt% of active material of positive electrode natural graphite, as binder 3wt% styrene fourth Diene rubber (SBR) mixes as the sheet non-type graphite of the CMC and 5wt% of the 1wt% of thickener and prepares anode slurry Material.Anode slurry is coated, is dried and pressed on copper base to form anode.
Polyethylene diagrams (thickness is inserted between the cathode and anode prepared as described above：25 μm) to form electrode list Member.Polyimide-based ion penetration barrier layer (thickness is inserted between electrode unit：30 μm), and stacked electrodes unit with Form electrode assembly.Electrode assembly is contained in bag simultaneously welding electrode lug plate.Inject electrolyte solution, then hermetic bag with Form secondary cell.
By by 1M LiPF6It is dissolved in EC/EMC/DEC (25/45/30；Volume ratio) in the mixed solvent come prepare electrolysis Then matter solution adds the vinylene carbonate of 1wt%, 1, the 3- propene sultones (1,3-propensultone) of 0.5wt% (PRS) and the dioxalic acid lithium borate of 0.5wt% (LiBOB).
Comparative example
The secondary cell of comparative example is manufactured by the method essentially identical with embodiment, the difference is that be omitted from Sub- penetration barrier layer.
Experimental example
Each embodiment and comparative example prepare five samples, and carry out penetrating assessment.Particularly, the electrode group based on stacking The quantity of part changes the quantity of ion penetration barrier layer while changing the capacity of secondary cell.
Each secondary cell is penetrated with the speed of 80mm/sec with the stainless steel lag screws of a diameter of 3mm, and measures and is determined as transporting The sample size of the battery of row failure.It will show irreversible damage or battery surface temperature be increased to 300 DEG C or more secondary Battery is considered as " failure ", and other secondary cells are considered as " normal ".As a result it is shown in the following table 1.
Table 1
With reference to table 1, in the comparative example of no ion penetration barrier layer, it is considered as event by penetrating assessment whole samples Barrier.However, in this example, when the quantity of the ion penetration barrier layer between electrode unit increases, penetrating reliability and being carried It is high.

Claims (15)

1. a kind of lithium secondary battery, including：
Multiple electrodes unit, each in the multiple electrode unit include first electrode, with the first electrode Separating layer polarity different polar second electrodes and be placed between the first electrode and the second electrode；And
At least one ion penetration barrier layer, between adjacent electrode unit, the gas permeability of the ion penetration barrier layer Less than the gas permeability of the separating layer.
2. lithium secondary battery according to claim 1, wherein the porosity of the ion penetration barrier layer is less than described point The porosity of absciss layer.
3. lithium secondary battery according to claim 1, wherein the separating layer includes by polyethylene, polypropylene, gathers inclined fluorine Polymer film prepared by least one of ethylene, polyethylene oxide and polyacrylonitrile, and
The ion penetration barrier layer includes polyester-based resin, polyurethane-based resin, polyimide-based resin, poly terephthalic acid Glycol ester, that is, PET, polymethyl methacrylate, that is, PMMA, fill organic and/or inorganic materials polypropylene screen and aromatic polyamides in It is at least one.
4. lithium secondary battery according to claim 1, wherein the first electrode and the second electrode about it is described from Sub- penetration barrier layer is relative to each other.
5. lithium secondary battery according to claim 1, wherein the ion penetration barrier layer is arranged in the electrode unit Between each space.
6. lithium secondary battery according to claim 5, wherein the first electrode and the second electrode are along the lithium The thickness direction of secondary cell is alternately relative to each other about the ion penetration barrier layer.
7. lithium secondary battery according to claim 1, further comprises：
Shell accommodates the electrode unit and the ion penetration barrier layer；
Electrolyte injects in the shell；And
First electrode lug plate and second electrode lug plate, respectively from each in the first electrode and the second electrode Extend to the outside of the shell.
8. lithium secondary battery according to claim 7, wherein the ion penetration barrier layer is along the lithium secondary battery Thickness direction it is be overlapped at least partly with the first electrode lug plate and the second electrode lug plate in the shell.
9. lithium secondary battery according to claim 8, wherein electrode connection panel region are limited to the end of the electrode unit Between portion and the shell,
The part of the ion penetration barrier layer extends to the electrode connection panel region.
10. lithium secondary battery according to claim 8, wherein the ion penetration barrier layer is in the first electrode wiring Length on the extending direction of piece and the second electrode lug plate be more than the separating layer in the first electrode lug plate and Length on the extending direction of the second electrode lug plate.
11. lithium secondary battery according to claim 8, wherein width direction of the separating layer in the lithium secondary battery On length be more than length of the ion penetration barrier layer in the width direction of the lithium secondary battery.
12. lithium secondary battery according to claim 11, wherein the separating layer by coupling part along the thickness Direction and the width direction are extended with zigzag shape.
13. lithium secondary battery according to claim 1, wherein the first electrode is including the first collector and is coated in institute The first electrode active material layer on the first collector is stated,
The second electrode includes the second collector and coated in the second electrode active material layer on second collector, and And
The first electrode active material layer and the second electrode active material layer be respectively coated on first collector and On two surfaces of second collector or single surface.
14. lithium secondary battery according to claim 13, wherein contacted with the ion penetration barrier layer described first Electrode includes the first electrode active material layer on the single surface coated in first collector, and
The second electrode contacted with the ion penetration barrier layer includes the single surface coated in second collector On the second electrode active material layer.
15. lithium secondary battery according to claim 14, wherein the ion penetration barrier layer is in direct contact described first Collector or second collector.
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